Method of preparing moisturproof materials



\ "tle and'crack upon crumbling. Even the best. 5

are re uire hunted 0 a, 1931.

PATENT-OFFIC mm mm OI BUFFALO, NEW YOBK AND KARI. OI"

CLEVELAND, OHIO, ASSIGNOBS '10 DU FONT GEE-1.02m COMPANY, YORK, I. Y, A. OOBPOMTION OI mmawm mnon or ranrnnma uors'runnrnoormrnarans mciornnw- Io Drawing. Original application filed January 8, 1927, Serial No. 1583 m. Divided and application met od of moistureproofing transparent materials, such as, for example, transparent sheets or films of regenerated cellulose without impairin the transparency of the base.-

.Many foo stuffs and other articles are wrapped in waxed paper to maintain them in t papers are waterproof and moisture roof the ordinary sense of the word an also in 'varyingdegrees'. They are, however, opaque or translucent, of appreciable thickness, britof them cannot be used where flexibility and .transp'arenc as well as moistureproofness if a base formed,

We live found that,

'for exam 1c, of a 'cellulosic material, and

a transparent material of which particular lms of regenerated cellulose are sheets or illustrative, is combined-as by being coated with a composition containing a minor quantity of a wa material and the coated 'material thensu jected to a temperature above the melting int of the waxy material in the composition, we can produce a productwhich is not only waterproof" but also moistureproof, flexible, non-,tacky,-odorless and cities of the base.

preferably also transparent.

It istherefore an object of this invention to provide a method of moistureproofing various basesincluding cellulosic materials and/or transparent bases without destroying or even impairing anv of the desirable prop- Other objects will appear from the fol- I lowing description and appended'claims.

In ac'cordancewith the principles of this invention a composition, preferably one containin a minor quantity of a waxy material, is app ied to the base formed of a cellulosic material, for example, transparent sheets or films of re nerated cellulose, and the coated material ried at an elevated temperature.

e original condition or state. Waxed Io. 808,818. ml divlllon divided and application fled Kay 8, 1831.

Preferably, the drying is carried out with warm air not exceeding 90 C. or 100 C.

'For optimum results the temperature of the of heat, in order to more thoroughly remove the lasttraces of asolvent and ma e the roduct entirely odorless, and/or a humidi ying atmosphere, for example, steam, for a short time to increase or restore the flexibility of the coated material.

In order to more clearly explain the invention, it will be described in connection with specific moistureplroofin compositions as hereinafter set fort It s to be understood that the invention is not restricted to the specific. compositions herein described,- since it is; apparent that the proportions of the ingredients may vary within wide limits,

depending partly on the characteristics desired in the product.

.In one of its modifications, the moisture- I proofing composition contains a minor. uan-- tity of a waxy material together with a ase, a gum or resin with or without a plasticizer dissolved in a suitable solvent.- By the term" solvent employed thisspecification is meant one or more solvents for derivatives either alone or admixed with one or more diluents to constitute what are com-" monly called solvent mixtures It is to be stituting the composition ma be mixed in different proportion depen g upon the qualities required in t e finished product;-

Ifor the base we prefer to usela cellulosic derivative such as a cellulose ester, and more articularlyanitrocellulose of the yroxyl ih type, because of its econom :1 though cellulose or an ether or example ethyl or other cellulose others may a.

' The beeswax,

be employed with satisfacto I results. The base is referably one yiel ing a solution of low viscosity, because this quality permits working with more highly concentrated solutions thancould be used with a base yielding1i a solution of high viscosity.

For t e gum we have found that gum dammar is. very-satisfactory, either singly or in combination with certain other gums. Some of the other gums that are preferably used either singly or 'in combination are ester gum, rosin, gum masticor the copal resins. It is to be understood that the either natural or synthetic, as it is possible to manufacture certain synthetic gums that are quite satisfactory substitutes for the natural ones. "ll he term resin employed herein and in the claims is intended to cover gums and resins both natural or synthetic, as above mentions For the war we prefer-to use a high. melting parafin wax as giving greater resistance to moisture than the low melting parafin. parafin being colorless and odorless is preferable to other wanes from these standpoints and also from the standpoint of economy. Examples of other waxes which may he used are oeresin, either hard or soft, and The above wanes may be used either singly or mixed with-each other or with other waxes as may be found desirable.

For the plasticizer we preferably employ one of the compounds or mixtures of compounds having a high boiling point and which are known as plasticizers or soiteners for cellulose esters or others, such as nitrocellulose cellulose acetate, ethyl cellulose, etc. We prefer to use a plasticizer which shall be substantially odorless and have obtained satisfactory results from using tri-cresyl phosphate, tri-phenyl phosphate, di-amyl phthalate or di-butyl phthalate, or castor oil.

The above ingredients, when used in the proper'prcpor'tions and with a suitable solvent, give a material which, after evaporation ofthe solvent at an elevated temperature, is not only moisture roof but which also is flexible without crac in which is perfectly transparent, which is dice from greasinose or tackiness, and which has the requisite tensile strength for the purposes to which it is desired that it be put.

The approximate limits may be given broadly as follows, the percentages being by weight 4 Per cent Base 30 toil) Resin 30 to 60 Wax- 2to 6 Plasticizer 5 to 30 The exact proportionsof the various ingredients will vary according to the qualities desired in the finished product, and these qualities will depend upon the use to which ms may be.

"easier to make and yet will have all the desired qualities xcelpt freedom from greasiness or tackin'ess'. varying the proportions of. the ingredients it is possible to obtain a compositlon with wide variations in the various qualities. By var ing the quantity of war we can obtain a wi e range in the degree of resistance to moisture; by varying t e quantity of or even omittin entirely the lasticizer, all degrees of fieni ility may be 0 tained; and by regulating the nature and quantity of the resin, wax and plasticizer, a wide range in the degree of transparency may be obtained. The plasticizer may also be omitted when the socalled plasticizing or softresins are employed as the resin component or the composition. It is to be understood that the invention is not restricted to the precise compositions hereinafter described, since it is apparent that the proportions of the ingredients may vary within wide limits depending partly on the characteristics desired in the product.

Hereafter there are set forth certain specific ratios of the proportions of ingredients which have been found satisfactory for Y suit, it resins of the hard type are used. We

have found that ratios within the limits or" 1:]. and 1:1 1; aresatisfactory for the hard type of resins.

The quantity of resin used depends upon the resin which is chosen, particularly with respect to its complete solubility and its ability to blend with the wax, and also the amount of base used with it. The preferred ratio of resin to base has been given above.,

A high ratio of hard resin to base renders the material brittle when used as a coating. A too low percentage of resin may result in a poor blending with the wax and thus a de-' crease of transparency and an increase in greasiness or tackiness.

The War preferably should be kept below 10% by weight of the total solids, and the best results are obtained when this percentage is kept between 2% and 6%. When the percentage approaches orexceeds 10%, crystal lization o'fjthe waxes may begin, thus decreasing transparency. However, the moisroportions and lfinds of v varied to obtain a. mix 7 0 tureproof' uality is notmaterielly affected, providing e same ratio of plasticizer to wax is retained and therefore a relatively large ntage of wax may be used when a relatigfly low degreeof' transparency is v -81 e. i I

The. amount of plasticizer desfnts than e egree on the cellulose derivative and flexibility desired in the product. 'It may depend in part on the amount of wax and also upon the ratio by weight of the amount of resin to the amount of base. When this ratio is relatively large, a ter quantity of plasticizer should be to overcome the brittle ness which is developed by the relatively large amount of resin. Moreover, the degree of moisture roofness may I depend partly upon the ratio. of the wax to the lasticizer and, therefore, this ratio partly etermines the percentage of plasticizer employed. The ratio of plasticizer to wax may' vary between the limits of 1:1 and 4: 1 with good results in the way ofjachieving-a moistureproof material.- v a Wehave discussed above the proper ratios of the hard variety of resin to the base and of plaaicize'r to wax. It now remains to discuss the referred ratio of the combined weights 0 base and resin to the combined weights ofwax-and plasticizers .The combined weights of baseand resinare usually several times-greater than the combined Wei hts of wax and plasticizer. The ratio of t e weights of base and resin combined to the weights of wax and plasticizer combined may vary between thslimits of about 2.3: 1.

' and :1, but we find thatthe referred ratio isbetween 4: 1 and 8:1. If t e ratio is less 4 than 2.3:'1 the-sheet or coating will either become tacky,'due to,the high percentage of plasticizer or will become 0 aque and greasy due to the high percentage 0 wax. When the" ratio of weights of resin and. base to plastiof the desirable properties already. e'numerated. In .this matter the choice is' defined by the above approximate limits, but,;the followso ing examples illustrate several excellent com-' binations which have been employed with success. --We haveclassed as solids'tlie ingredients of the composition which are dissolved in-a solvent for the purpose of manufaeturing the finished article; While the .mg after it is'dlg "and percentages of the solid ingredients.

. mix to forms. clear film but-by a pro r choice of uantit and kind of resin, it as non-tacky the wax .u to 50% or over by weight, in or-.

- lasticizer may ap as "aliq uid, nevertheess, it is non-vole sand remains in the coatand therefore, for the purpose of this ap cetion an'dfor convenience, alias: the ingredients are referred to as so 1 sous constituent Exam le 1:

Nitrocellulose a 62 155156! gum Di-butyl phthalate 8.7. Parafiin 4.3

Example2:

' Nitrocellulose 60. Gum dammar 84 Tri-cresy'l phosphate; 12 Paraffin;- I s 4 The above formulas are ven merely as exemplary and it is to be un c arstood thatwe do not consider ourselves limited thereby. Other formulas ma be develo -by those skilled in thear't w en taught y the above dis f lpsure. f ed' e composition is orm -b m t 0-" gather the ingredients in the desired percentage which-ma be fixed upon for the particularpurposes or which the product is to be,

used. The mixture-is then dissolved, using preferably anywell known organic solvent which is readi' y volatile and will consequent- 7 ly evaporate rapidly. The particular solvent used is determined chiefly with reference to the method of application andto the'nature The solvent must be such as to retain all of the solid ingredients in a homogeneous solu-' tion. The wax and base ordinarily do not been foun .possi Is to' make the combined resin and wax mix with the base and plasticizer. The solvent must then be chosen to retain the resin, wax, baseand. plasticizer in their proper proportions in complete solution, so'that upon evaporation of the solvent a moisture roof, transparent, flexible and is produced. v It is usual to employ solvent materials for der to ma ntain the wax in solution during the process of of'the coating or sheet. Generally speakm also, it is economical to engsloy relatively} ow percentages of inter m ate boiling solvents for nitrocellulose. Bfy employing these solvents in a proportion o 10% and under of the total solvent,-we re vent too rapid drying-of the coating w 'ch would cause cooling ofthe surroundingatmosphere and precipitation of water vapor on the material.

While the particular solvent must determined separately for the particular composition, we give below thespecific solvent is.

combinations which we have found may be used with the respective examples of compositions given above.

Per cent based Solvent for Example 1: $32, 2:? Alcohol 25 Ether--- 43 Toluene 18 Butyl acetate 14 Solvent for Example 2:

Ethyl acetate 62 Toluene 27 Alcohol 9 Butyl acetate 2 The solution may be used in a variety of ways. It may be cast by known methods into thin sheets which, after being heated m accordance with this invention, are transparent, flexible, have, the required tensile strength and at the same time are several times more moist-ureproot than anything hitherto knownthat have the other qualities mentioned above. .The films will have the ability to resist the transmission or difiusion of water vapor to an extent at least 3times as great as that displa ed by films ofequal thickness and produce from cellulose ester lacquers heretofore formulated without admixture of waxes'or wax-like materials when tested under the same conditions. It is to be understood that the value 3 merely sets forth the minimum improvement and in nowise limits the higher degrees of moistureproofing that can .be obtained. The compositions, herein described, are inherently capable in.

many formulations prepared according to he disclosure herein set forth, of producing r2 .1 showing an improvement over the prior art films of not only 3 but 10, 20, 40 and in some cases 100 fold. This is an efiect which has been heretofore impossible to secure with cellulose ester lacquers formulated in the usual way with gums, resins,'oil s, plasticizers, etc.,

but without waxes or wax-like materials.

Again thesolution may be applied in the form of a coating of sheets or films of cellulose regenerated from viscose, the coating being done by; suitable machines. In accordance with this process which constitutes the present invention, after the sheet or filmpf regenerated cellulose has been coated w th the composition, it is dried preferably with warm air of a temperature not exceedlng 90 C. or 100 C. It'is preferable to keep the temperature of the air above the melting or crystallization point ofthe wax or waxes in the compositiomhereinafter referred to as the melting point of thewax or waxes in the composition, thereby preventing separation or crystallization of the wax during the drying operation. It is also preferable to use air low in moisture content to aid in the evaporation of the solvent. Subsequent to the drying, the product is preferably sub- 'ase teac es jected to the action of heat for a short time m-orderto more thoroughly remove the last traces ot the solvent and thus make the product entirely odorless. Preferably, the coated after is subjected to the action of a hot humidi ying atmosphere to restore or increase'the flexibility of the product and to aid-in the elimination of residualsolvents. Sheets or films of regeneratedcellulose may be coated on .one or oth sides, the coating being from .00005" to .0005" thick or thicker. In practice it' has been found that it is sufiicient to apply a coating .0001" to each side of the sheet or film of regenerated cellulose, When such materials are submitted to standard tests, the results clearly indicate that said product or film of regenerated cellulose will gield a product which is at least 7 times 'ective in resisting the transmission of moisture or water vapor therethrough as the uncoated sheets or films when tested under thesame conditions. The value merely indicates the minimum improvement and noshow not onlyv 7' but 25, 50, 100 or even several hundred times the resistance to the passage of moisture or water vapor, as will the uncoated sheet when tested under thesame conditions. Moreover, the final product retains all. of the desirable characteristics in-' cluding transparency and flexibility posseilsepl by the sheets or films of regenerated ce u use.

, lit it is desired to produce a colored prodnot, a coloring agent, such as a pigment or dye, may be added to the coating solution. Though the above specific description relates to the treatment of sheets or films of -regenerated cellulose, it is apparent that the method is equally-applicable to other materlals, such as, for example, paper, fabrics, leather, metal etc. a

By the term molstureproof or its equivalent as applied to the films or protective coatings herein described, we mean the ability to resist the transmission or diffusion of moisture or water vapor to an ex cut at least 3 times as great as that displayed by films or coatings of equal thickness and produced from cellulose ester lacquers heretofore formulated without the admixture thereto ofwaxes or wax-like materials when testedunder the same conditions and/ or when applied to sheets or films of regenerated cellulose or other cellulosic 'base to yield a product which is atleast 7 times as efiective in resistin the transmission or diffusion of moisture t erethrough asthe uncoated sheets when tested under the same conditions.

. It should be understood that the above definition merely sets forth the minimum provements inmoistureproofing efiect which can be obtained from the invention and that the compositions are inherently capable, in

- many formulations according to the disclosures here set forth, of producing films showing an improvement over prior art coatings of not only 3, but 10, 20, 40. and in some cases even 100 fold. This is an efl'ect which has not been heretofore possible to obtain with cellulose ester lacquers formulated in the usual way with gums, resins, oils. plasticizers,

' etc. but without waxes or wax-like materials.

When applied to regenerated cellulose or other cellulosic base, a coated sheet is obtained by the/invention which will readily show not only 7 but as much as 25, 50, 100, or in some cases several hundred times the reslstance to the passage of moisture vapor as will the uncoated sheet when tested under the same conditions. that the figures set forth in the above defini tron are in nowise limiting in respect to the higher degrees of moistureproofing that can be obtained. This application'is a division of a plication Serial No. 308,873 filed Sept. 2 1928 which is in turn a division of application Ser1al No. 158,816 filed Jan. 3, 1927.

" We claim; i

1. A method of preparing a moisturepro'of .-material which comprises applying a'composition containing a minor quantity of a waxy substance to a base and subjecting the coated material to a temperature above the melting point of the waxy substance in the composition. I

2. A method of preparing a moistureproof material which comprises applying a composition containing a minor quantity of a waxy substance to a base of a cellulosic material and subjectingthe coated material to a temperature above the melting point of the waxy substance in the composition.

3. A method of' preparing a transparent moistureproof material which comprises applying a composition containing a minor quantity of a waxy substance to a transparent base and subjecting the coated material to a temperature above the melting point of the wax in thecomposition. I

4.; A method ofpreparing a transparent moistureproof material which comprises applying a composition containing a minor (piantity of a waxy substance to a transparent s eet or film of regenerated cellulose and subcomposition.

5. A method ofpreparing a moistureproof.

material which. comprises applying a composition containing a minor quantity of a waxy substance to a base andsubjecting the coated material to a temperature-above the melting point of the waxy substance in the composition. and heating the dried material.

6. A method of preparing a moistureproof It is therefore evident substance to a base of a cellulosic material and subjecting the coated material to a temperature above the meltin point of the waxy substance in the compositlon, and heating the dried material.

7. A method of preparing a transparent moistureproof material which comprises applying a composition containing a minor quantity of a waxy substance to a transparent base and subjecting the coated material to a temperature above the melting point of the wax in the composition, and heating the dried material.

8. A method of preparing a transparent moistureproof material which'comprises applying a composition containing a minor uantity of a waxy substance toa transparent s 'eet or film of retgenerated cellulose and subjecting the coate material to a temperature above the melting point of the wax in the composition, and heating the dried material.

9. A method of preparing a moistureproof material which comprises applying a composition containing aminor quantity of a waxy substance to a base and subjecting the coated material to a temperature above the melting point of the waxy substance in the composition, and subjecting the dried material to a humidifying treatment.

10. A method of preparing a moistureproof material which comprises applyinga composition containin a minor quantity of a waxy substance to a ase of a cellulosic material and subjecting the coated material to a temperature'above the meltin point of the waxy substancein the composition, and subjecting the dried material to a humidlfy ng treatment.

11. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose deriva- I tive, a wax and a solvent to a sheet or film of a' cellulosic material and evaporating the solvent at a temperature above the melting point vent at a temperature above t e melting point of the wax in the composition in an atmosphere having a low moisture content.

a 13. A method of preparing a moistureproof material which comprises appl 'ng a composition comprising a cellulose erlvative, a wax and a solvent'to a sheet or film of a cellulosic material, evaporating the solvent at a temperature above the melting oint of the wax in'the composition and su jeeting the dried product to the action of heat.

' 14. A method of preparing a moistureproofmaterial which comprises applying a 5 the wax in the composition in an atmos here having a low moisture content and su jecting the dried product to the action of heat.

15. A method of preparing a moistureproof material which comprises applying a a composition comprising a cellulose derivative, a wax and a solvent to a sheet or film of a cellulosic material, evaporating the solvent at a temperature above the melting point of the wax in the composition and. subjecting the dried product to a humidifying treatment.

16. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a wax and a solvent to a sheet or film of a cellulosic material, evaporating the solvent at a temperature above the melting point of the wax in the composition in an atmosphere havinga low moisture content and subjecting the dried product to a humidifying treatment.

17. A method of preparing a transparent moistureproof material which comprises applying a composition containing a minor quantity of a waxy substance to a transparent base and subjectingthe coated material to a temperature above the melting point of the wax in the composition, and subjecting the dried material to a humidifying treatment.

18. A method of preparing a transparent moistureproof-material which comprises applying a composition containing a minor quantity of a waxy substance to a transparent sheet or film of regenerated cellulose and subjecting the coated material to a temperature above the melting point of the wax in the composition, and subjecting the dried mate- .rial to a humidifying treatment.

19. A method of preparing a moistureproof material which comprises forming a film of a solution comprising a cellulose derivative and a wax and evaporating the solventat a temperature above the melting point of the wax in the composition.

20. A method of preparing a moistureproof material which comprises Forming a film of a solution comprising a cellulose derivative and a wax. evaporating the solvent at a temperature above the melting pointof thewax in the composition in an atmosphere having a low moisture content.

21. A method of preparing a moistureproof material which comprises forming a film of a solution comprising a cellulose derivative and a wax, evaporating the solvent at a temperature above the melting point of the wax in the composition and subjecting the dried product to the action of heat.

- 22. A method of preparing a moisture proof material which comprises forming a film of a solution comprising a cellulose dc:

rivative and a wax, evaporating the solvent at a temperature above the melting point of the wax in the composition in an atmos here having a low moisture content and su jecting the dried product to the action of heat.

23. A method of preparing a moistureproof material which comprises forming a film of a solution comprising a cellulose derivative and a wax, evaporating the solvent at a temperature above the melting point of the wax in the composition and subjecting the dried product to a humidifying treatment.

24. A method of preparing a moistureproof material which comprises forming a film of a solution comprising a cellulose derivative and a wax, evaporating the solvent at a temperature above the melting point of the wax in the composition in an atmosphere hav ing a low moisture content and subjecting the dried product to a humidifying treatment.

25. A method of preparing a moistureproof material which comprises forming a film of a solution comprising a cellulose derivative, a resin, a wax and a plasticizer and evaporating the solvent at a temperature above the melting point of the wax in the composition.

26. A method of preparing a moistureproof material whichcomprises forming a film of a solution comprising a cellulose derivative, a resin, a wax and a. plasticizer and evaporating the solvent at I a temperature above the melting point of the wax in the composition in an atmosphere having a low moisture content. r

27. A method of preparing a moistureproof' material which comprises forming a film of a solution comprising a cellulose derivative, a resin. a wax and a plasticizer, evaporating the solvent at a temperature above the melting point of the wax in the composition and subjecting the dried product to the action of heat.

28. A method of preparing a moistureproof material which comprises forming a film of a solutioncomprising a cellulose derivative, a resin. a wax. and a plasticizer, evaporating the solvent at a temperature above the melting point of the wax in the composition in an atmosphere having a low moisture content and subjecting the dried product to the action of heat.

29. A method of preparing a moistureproof material which comprises forming a filmpf a solution comprising a cellulose derivative, a resin, a wax and a plasticizer, evaporating the solvent at a temperature above the melting point of the wax in the composition and subjecting the dried product to a humidifying treatment.

30. A method of preparing a moistureproof material which comprises forming a film of a solution comprising a cellulose derivative, a resin, .a wax and a plasticizer, evaporating the solvent at a temperature above the melting point of the wax in the proof material which comprises applginga composition in an atmosphere having a low moisture content and subjecting the dried product to a humidifying treatment.

' 31. A method of preparing a moistureproof material which, comprises applying a composition comprising a cellulose derivative, a wax and a solvent to a sheet or film of regenerated cellulose and evaporating the Q solvent at a temperature above the melting point of the wax in the compositlon.

32. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a wax and a solvent to a sheet or film of regenerated cellulose and evaporating the solvent ata temperature above the melting pomt of the wax in the composition in an atmosphere having a low moisture content.

33. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a wax and a solvent to a sheet or film of regenerated cellulose, evaporating the solvent 25 at a temperature above the meltlng point of the wax in the composition and subjecting the dried product to the action of heat.

34. A method of preparing a moistureproof material which comprises applying a 3'0 composition comprising a cellulose derivative, a wax and a solvent to a sheet or film of regenerated cellulose, evaporating the solvent at a temperature above the melting polnt of the wax in the composition in an atmosphere having a low moisture content and subjecting the dried product to the action of heat.

35. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a wax and a solvent to'a sheet or film of regenerated cellulose,-evaporatin the solventata temperature above the melting point of the wax in the composition and subjecting the'dried product to a humidifying treatment.

36. A method of preparing a moistureproof material which comprises applying a composition comprisinga cellulose derivative, a Wax and a solvent to a sheet or film of regenerated cellulose, evaporating the solvent at a temperature above the melting point of the wax in the composition in an atmosphere having a 10W moisture content and subjecting the dried product to a humidifying treatment.

37. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a resin, a wax, a plasticizer and a solvent to a sheet or film of regenerated cellulose and evaporating the solvent at a temperature above the melting point of the wax in thecomposition.

38. A method of preparing a moisturecomposition comprising a cellulose erivative, a resin, a wax, a lasticizer ands solvent to a sheet or film o regenerated cellulose and evaporating the solvent at a temperature above the melting point of the wax in the composition in an atmosphere having a low moisture content.

39. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a wax, a resin, a plasticizer and a solvent to a sheet or film of regenerated cellulose, evaporating the solvent at a temperature above the melting point of the wax in the composition and subjecting the dried product to the action of heat.

40. A method of preparing a moistureproof'material which comprises applying a composition comprising acellulose derivative, a wax, a resin, a plasticizer and a solvent to a sheet or film of regenerated cellulose, evaporating the solvent at a temperature above the melting point of the wax in the composition in an atmosphere having a low moisture content and subjecting the dried product to the action of heat.

41. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a wax, a res n, a plasticizer and a solvent to a sheet or film of regenerated cellulose, evaporating the solvent at a temperature above the melting point ofthe wax in the composition and subjecting the dried product to a humidifving treatment.

42. A method vof preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a wax, resin, a plasticizer and a solvent to a sheet or film of regenerated cellulose, evaporating the solvent at a temperature above the melting point of the wax in the composition in an atmosphere having a low moisture content and subjecting the dried product to a humidifying treatment.

43. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative. a resin. a wax. a plasticizer and a solvent to a sheet or film of a cellulosic material and evaporating the solvent at a temperature above the melting point of the wax in the composition.

44. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a resin, a wax, a plasticizer and a solvent to a sheet or film of a cellulosic material and evaporating the solvent at a temperature above the melting point of the wax in the composition in an atmosphere having a low moisture-content.

45.' A method of preparing a moisture- 139 proof material which comprises applying a composition comprising a cellulose derivative, a wax, a resin, a plasticizer and a solvent to a sheet or film of a cellulosic material, 5, evaporating the solvent at a temperature abovevthe melting point of the wax in the composition and subjecting the dried product to the action ofheat.

46. A method of preparing a moisture- 3e proof material which comprises applying a composition comprising a cellulose derivative, a wax, a resin, a ,plasticizer and a solvent to a sheet or film of a cellulosic material, evaporating the solvent at a temperature at above the melting point of the wax in the composition in an atmosphere having a low moisture content and subjecting the dried product to the action of heat.

47. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a wax, a resin, a plasticizer and a solvent to a sheet or film of .a cellulosic material, evaporating the solvent at a temperature fie above the melting point of the wax in the composition and subjecting the dried product to a humidifying treatment.

48. A method of preparing a moistureproof material which comprises applying a compo- 86 sition comprising a cellulose derivative, a Wax, a resin, a plasticizer and a solvent to a sheet or film of a cellulosic material, evaporating the solvent at a temperature above the melting point of the wax in the composition 1 in an atmosphere having a low moisture content and subjecting the dried product humidifying treatment.

49. A method of preparing a moistureproot material which comprises forming a film of a solution comprising a cellulose derivative, a resin and a wax and evaporating the solvent at a temperature above the melting point of the wax in the composition.

50. A method of preparing a moistureproof material which comprises forming a film of a solution comprising a cellulose derivative, a resin and awax and evaporating the solvent at a temperature above the melting point of the wax in the composition in an atmosphere having a low moisture content.

51. A method of preparing a moistureproof material which comprises forming a film of a solution comprising a cellulose derivative, a resin and a wax, evaporating the solvent at a temperature above the melting point of the wax in the composition and subjecting the dried product to the action of heat.

52. A method of preparing a moistureproof material which comprises forming a film of a solution comprising a cellulose derivative, a resin and a wax, evaporating the solvent at a temperature above the melting point of the wax in the composition in an attoa aeaaeee mosphere having a low moisture content and 1sub ecting the dried product .to the action 0 ieat.

53. A method of preparing a moistureproof material which comprises forming a film of a solution comprising a. cellulose de-' rivative, a resin and a wax, evaporating the solvent at a temperature above the me ting oint of the wax in the composition and subecting the dried product to a humidifying treatment.

54. A method of preparing a moistureproof material which comprises forming a film of a solution comprising a. cellulose derivative, a resin and a wax, evaporating the solvent at a temperature above the melting point of the wax in the composition in an atmosphere having a low moisture content and subjecting the dried product to a humiditying treatment.

55. A method of preparing a moistureproof material which comprises forming a film of a solution comprising a cellulose derivative, a resin and a wax, evaporatin the solvent at a temperature above the me ting point of the wax in the composition in an atmosphere having a low moisture content and heating and humidifying the dried material;

56. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a resin, a wax and a solvent to a sheet or film of a cellulosic material and evaporating the solvent at a temperature above the melting point of the wax in the composition.

57. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a resin, a wax and a solvent to a sheet or film of a cellulosic material and evaporating the solvent at a temperature above the melting point of the wax in the composition in an atmosphere having a low moisture content.

58. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose erivative, a wax, a resin and a solvent to a sheet or film of a cellulosic material, evaporating the solvent at a temperature above the melting point of the wax in the composition and subjecting the dried product to the action of heat.

59. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a wax, a resin and a solvent to a sheet or film of a cellulosic material, evaporatingv the solvent at a temperature above the melting point of the wax in the composition in an atmosphere having a low moisture content and glubjecting the dried product to the action ofeat.

60. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivasolvent at a temperature above-the me oint of the waxin the composition and spbecting the ,dried product to a humidifymg treatment.

- 61. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose erivative, a wax, a resin and a solvent to a sheet or film of a cellulosic material. evaporating the solvent at a temperature above the melting point of the wax in the composition in an atmosphere having a low moisture content and subjecting the dried product to a humidifying treatment.

62. A method of preparing a moisture proof material which comprises applying a composition comprisin a cellulose erivative. a wax, a resin an a solvent to a sheet.

or film of a cellulosic material, evaporating thesolvent at a temperature above the melt-. ing point of the wax in the composition and heating and humidifying the coated material.

63. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a resin, a wax and a solvent to a sheet-or film of regenerated cellulose and evaporating the solvent at a temperature above the melting point of the wax in the composition.

64. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative. a resin, a wax and a solvent to a sheet or film of regenerated cellulose and evaporating the solvent at a temperature above t e melting point of the wax in the composition in an atmosphere having a low moisture content.

65. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative. a wax, a resin and a solvent to a sheet or film of regenerated cellulose,-evaporating the solvent at a temperature above the melt ing point of the wax in the composition and iubjecting the dried product to the action of eat.

66. A method of preparing a moisture proof material which comprises applying a composition comprising a cellulose derivative. a wax, a resin and a solvent to a sheet or film of regenerated cellulose, evaporating the solvent at a temperature above the melting point of the wax in the composition in an atmosphere having a low moisture content and subjecting the dried product to the action of heat.

67. A method of preparing a moistureproof material which comprises appl ing a composition comprising a cellulose erivative, a wax, a resin and a solvent to a sheet or film of regenerated cellulose, evaporating the solvent at a temperature above the melting oint of the wax 1n the composition and subecting the dried product to a humidifying treatment, v

68. A method of preparing a moistureproof material which comprises appl a composition comprising acellulose derivative, a wax, a resin and a solvent to a sheet or film of regenerated cellulose, evaporatin the solvent at a temperature above the me ting point of the wax in the composition in an atmosphere havin a low moisture content and subjecting the ried product to ahumidifying treatment. i

69. A method of preparing a moisture-' proof material which comprises appl -ng a composition comprising a cellulose e rivative, a wax, a resin and a solvent to a sheet or film of regenerated cellulose", eva rating the solvent at a temperature above t emeltmg oint of the wax in the composition and heating andhumidifying the dried product.

70. A method of preparing a moistureproof material which comprises applying a composition containing a minor uantity of a waxy substance to a base and su bject-ing the coated material to a temperature above the melting point of the waxy substance in the composition, and heating and humidifying the dried material. 7

71. A methodof preparing a moistureproof material which comprises applying a composition containing a minor quantity of a waxy substance to a base of a cellulosic materm] and subjecting the coated material to a temperature above the melting point of the waxy substance in the composition, and heating and humidifying the dried material.

72. A method of preparing a transparent moistureproofmaterial which comprises applying a composition containing a minor quantlty of a waxy substance to a transparent base and subjecting the coated material to a temperature above the melting point of the wax in the composition, and heating and humidifying the dried material.

73. A method of preparing a transparent moistnreproof material which comprises applying a composition containing a minor quantity of a waxy substance to a transparent sheet or film of regenerated cellulose and sub- I proof material which comprises forming a film of a solution comprising a-cellulose derivative and a wax, evaporating the solvent at a temperature above the melting point of the wax in the composition and heating and humidifying the dried'product.

75. 'A method of preparing a moistureproof material which comprises forming a film of a solution comprising a cellulose derivative, a

resin, a wax and a plasticizer, evaporating the solvent at a temperature above the'melting point of the wax in the composition and heating and humidifying the dried product.

'5 76. A method of preparing a moistureproof material which comprises applying a composition comprising a cellulose derivative, a wax and a solvent to a sheet or film oi regenerated cellulose,.exaporating the solvent at a temperature above the melting point ot the wax in the composition and heating and humidifying the dried product.

77. A method of coating which comprises applying'a moistureproofing solution comprising a cellulose (lGI'lVitlllV8 &-WHX and a solvent to a base. and evaporating the solvent at a temperature above the melting point of the wax in the composition.

78. A method of coating which comprises applying a moistureproofing solution comprising a cellulose derivative, a wax, a resin and a solvent to a base. and evaporating the solvent at a temperature above the melting point of the wax in the composition.

79. A method of coating which comprises applying a moistureproofing solution comprising a cellulose derivative. a wax, a resin. a plasticizer and a solvent to a base, and

-evaporating the solvent at a temperature above the melting point of the wax in the.

composition.

80. A method of coating which comprises applying a moistureproofing solution comprising a cellulose derivative. a wax and a solvent to a base. evaporating the solvent at a temperature above the melting point of the wax in the composition. and heating the dried material.

81. A method of coating which comprises 40 applying a moisture-proofing solution 'com prising a cellulose derivative. a wax, a resin and a solvent to a base. evaporating the solvent at a temperature above the melting point p of the wax in the composition, and heating the dried material.

82. A method of coating which comprises applying a mfoist-ureproofing solution comprising a cellulo e derivative. a wax. a resin, a plasticizer and asolvent to a base. evaporating the solvent at a temperature above the melting point of the wax in the. composition, and heating the dried material.

83. A method of coating which comprises applying a moistureproofing solution comprising a cellulose-derivative and a wax to a base. and heating the coated base in an atmosphere at a temperature above the melting point of the wax in the composition.

84. A method of coating which comprises applying a moistureproofing solution comprising a cellulose derivative. a gum -and a wax to a base. and heating the coated base in' an atmosphere at a temperature above the melting point of the wax in the composition.

plasticizer and a wax to a base of a cellulosic masses 85. A method of coating which comprises applying a moistureproofing solution comprising a ellulose derivative, a gum, a plasticizer and a wax to a base, and heating the coated base in an atmosphere at a temperature. above the melting point of the wax in the composition.

86'. A method of coating which comprises applying a moistureproofing solution comprising a cellulose derivative and a wax to a base ot' a cellulosic material, and heating the coated base in an atmosphere at a temperature above the melting point of the wax in the composition.

87. A method of coating which comprises applying a moistureproofing solution comprising a cellulose derivative, a gum and a wax to a'base of a cellulosic material, and heating the coated base in an atmosphere at a temperature above the melting point of the wax in the composition.

88. A method of coating which comprises applying a moistureproofing solution comprising a cellulose derivative, a gum, a

material, and heating the coated base in an atmosphere at a temperature above the melting point of the wax in the composition.

89. A method of coating which comprises applying a moistureproofing solution comprising a cellulose derivative and a wax to a sheet or film of regenerated cellulose, and

heating the sheet or film in an atmosphere'at a temperature above the melting point of the wax in the composition.

90. A method of coating which comprises applying a moistureproofing solution comprising a cellulose derivative, a gum and a wax to a sheet or film or regenerated cellulose, and heating the coated sheet or film in an atmosphere at a temperature above the melting point of'the wax .in the comosition.

' 91. A method of coating which comprises applying a moistureprooting solution conipa" prising a cellulose derivative, a guru, a plasticizer and a wax to a sheet or film of regenerated cellulose, and heating the coated sheet or film in an atmosphere at a temperature above the melting point of the wax in ms the composition. a

' lln testimony whereof. we have aiiixed our signatures to this specification.

WILLIAM HALE QHARCH.

KARL EDWIN PRINDLE. to

rat

CERTIFICATE OF CORRECTION.

Patent No. 1,826,699. Granted October 6, rest, to

WILLIAM H. CHARCH ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, lines 87 and 8f "pyroxylin"- should be hyphenated; page 4, line 47, for the word "of" second oc currence read to; line 115, for "ex ent" read extent; page 10, line 9, claim 7t for the misspelled word "exaporating" read evaporating; line 104, claim 90, fo: the word "or" first occurrence read of; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office. e a

Signed and sealed this 3rd day of November, 'A. D. 1931.

M. J. Moore, (Seal) Acting Commissioner'of Patents.

CERTIFICATE OF CORRECTION.

Patent No. 1,826,699. Granted October 6, 1931, to

WILLIAM HALE CHARCH ET AL.

It is hereby certified that Certificate of Correctionissued November 3. 1931, was erroneously drawn as to line 104, claim 90, and that this line should read "wax to a sheet or film of regenerated cel-"; and that the said Certificate should be read withthis correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 10th day of November, A. D. 1931.

M. J. Moore,

(Seal) Acting Commissioner of Patents. 

